Collision-induced dissociation studies on Fe(O2)n(+) (n = 1-6) clusters: application of a new technique based on crossed molecular beams.

Gas-phase oxygen-rich iron oxide clusters Fe(O2)n(+) (n = 1-6), are produced in a molecular beam apparatus. Their stability and structure are investigated by measuring the fragmentation cross-sections from collision-induced-dissociation experiments. For this purpose, two different techniques have been employed. The first one relies on the measurement of the fragments resulting after collisional activation and subsequent dissociation of mass selected cluster ions in a molecular beam passing through a cell filled with noble gas atoms. The second one is a new approach that we introduce and is based on crossed molecular beams to measure the fragmentation cross-sections, in a more efficient manner without mass selection of the individual clusters. The cross-sections obtained with the different techniques are compared with each other as well as with theoretical ones resulting from the application of a simple geometrical projection model. Finally, the general trends observed are compared with results for other Fe-molecule clusters available in the literature.

Charge-transfer processes in the assembly of Si(n)O(m) neutral clusters.

The chemical bond formation in oxygen-rich Si(n)O(m) clusters was investigated by sampling the potential energy surface of the model systems SiO + SiO(2) → Si(2)O(3) and (SiO)(2) + SiO(2) → Si(3)O(4) along a two-dimensional reaction coordinate, by density functional theory calculations. Evidence for crossing between the weakly bound neutral-neutral (SiO)(n) + SiO(2) and the highly attractive ion-pair (SiO)(n)(+) + SiO(2)(-) surfaces was found. Analysis of frontier molecular orbitals and charge distribution showed that surface crossing involves transfer of valence electron charge from (SiO)(2) to SiO(2). The sum of the natural atomic charges over the (SiO)(n) and (SiO(2)) groups of the Si(n)O(m) cluster products, gave a net positive charge on the (SiO)(n) "core" and a net negative charge on the (SiO(2)) groups. This is interpreted as the "ion-pair memory" left on the Si(n)O(m) products by the charge-transfer mechanism and may provide a way to assess the role of charge-transfer processes in the assembly of larger Si(n)O(m) neutral clusters.

Laser microperforated biodegradable microbial polyhydroxyalkanoate substrates for tissue repair strategies: an infrared microspectroscopy study.

Flexible and biodegradable film substrates prepared by solvent casting from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) solutions in chloroform were microperforated by ultraviolet laser ablation and subsequently characterized using infrared (IR) microspectroscopy and imaging techniques and scanning electron microscopy (SEM). Both transmission synchrotron IR microspectroscopy and attenuated total reflectance microspectroscopy measurements demonstrate variations in the polymer at the ablated pore rims, including evidence for changes in chemical structure and crystallinity. SEM results on microperforated PHBHV substrates after cell culture demonstrated that the physical and chemical changes observed in the biomaterial did not hinder cell migration through the pores.

Minimally invasive automated de-epithelization by precise ArF excimer laser ablation.

OBJECTIVE: Development of a robotic ArF excimer laser device with a three-dimensional (3D) pattern scanning sensor for the controlled de-epithelization of live mouse and xenografted epidermis. SIGNIFICANCE: The animal model could be adapted to humans for automated, minimally invasive de-epithelization of cutaneous areas and therefore is of interest for cutaneous gene therapy research. MATERIALS AND METHODS: Ablation thresholds of mouse, porcine, and human skin were measured by acoustic detection methods. These ablation thresholds were used as initial parameters for dosimetry measurements. De-epithelization of live mouse and xenografted epidermis was performed by laser ablation (ArF excimer laser, λ = 193 nm, t(p) = 20 nsec). The rectangular shape of the laser spot and a robotic arm displacement incorporating a three-dimensional patter scanning sensor allowed a polygonal tile floor irradiation of a 2-cm-diameter area. Ablated epidermis was subjected to histology. RESULTS: SCID and nude mouse skin did not entirely reflect the de-epithelization of human skin because abundant pockets of dermal keratinocytes persist in the outer root sheath of hair and cysts providing competitive foci of re-epithelization. Automated de-epithelization of human and porcine skin xenografts resulted in precise removal of keratinocytes with subcellular precision, providing a smooth live surface where epidermal transplants might engraft with little endogenous competition from residual outer root sheath from rare hairs. CONCLUSIONS: The displacement of the ArF excimer laser devices allows reproducible, smooth, and damage-free ablation of epidermal areas in the animal model.

Silicon oxide cluster formation and stability in the laser ablation of SiO targets.

The formation mechanism and stability of silicon oxide clusters observed in the ablation of SiO targets at 266 nm were investigated by time-of-flight mass spectrometry, laser-induced fluorescence (LIF), and DFT calculations. Neutral and positively charged Si(n)(+/0) and Si(n)O(m)H(0,1)(+) clusters were identified in the plume, but neutral Si(n)O(m) could not be observed. The time distribution of SiO in the plume measured by postionization with an ArF laser (Delta lambda approximately 1 nm, tau approximately 14 ns) and mass spectrometric detection was compared with that obtained by LIF with narrowband dye laser selective excitation of one specific rovibronic transition in SiO. Postionization leads to a multicomponent distribution that extends up to times near 100 micros after ablation, whereas LIF measurements obtain time distributions shorter than 20 micros. DFT calculations of several Si(n)O(m)(0/+) were performed, showing that one photon absorption of the postionization laser makes available low-energy dissociation channels of the neutrals, whereas two photon absorption is required for ionization. DFT calculations were carried out for stoichiometric H-containing clusters Si(n)O(n)H(+) (n = 1-4). For n = 1,2, the optimized geometries involve bonding of hydrogen to one oxygen atom in the clusters; for n = 3 and 4, the structures containing H-Si bonds are more stable.

A Nd:YAG laser-microperforated poly(3-hydroxybutyrate-co-3-hydroxyvalerate)-basal membrane matrix composite film as substrate for keratinocytes.

Epithelia cultured for the treatment of ulcers, burns and for gene therapy applications require a flexible biomaterial for growth and transplantation that is adaptable to body contours. We tested several materials and found that a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBHV) polyester provided support for keratinocytes, although adhesion to this material proved to be suboptimal. Since epithelia adhere to the mesoderm through basal membranes, we engineered a basal membrane surrogate by preparing composites of PHBHV with basal membrane matrix (BMM). To allow cell migration into injuried areas the polyester film was micromachined to insert high-density micropores through a Nd:YAG laser ablation process. These flexible composites provided firm attachment for keratinocytes from the outer root sheath of human hair allowing keratinocyte migration through micropores. Films of microperforated PHBHV-BMM may be of use for the replacement of diseased or injured skin epithelia.